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7. Dry Lab III: Molecular Symmetry

Topics:

1. Motivation

2. Symmetry Elements and Operations

3. Symmetry Groups

4. Physical Implications of Symmetry

1. Motivation

Finite symmetries are useful in the study of molecules. They are used in the classification of molecules, simplifying quantum mechanical calculations on molecules, determining the presence of certain molecular properties such as molecular polarity and chirality. In the next two dry labs, we will focus on finite symmetries and

groups of finite symmetry operators. We will use P.W. Atkins, Physical

Chemistry, Chapter 15, as our principle reference. Another book by F.A. Cotton, entitled Chemical Applications of Group Theory, either the first or second edition, is an excellent source book too. In Chemistry 331/333, you have had some exposure to finding symmetry elements and symmetry operations. This Dry Lab is meant to

 be a either a practical review or an introduction to symmetry elements and symmetry operations.

The set of all symmetry operations for a

molecule form a mathematical structure called a group. Here, we will look at group structure, classes of symmetry operations, and the naming

of molecular point groups. We will examine

how to use the group structure to predict when a molecule is polar or chiral. You will apply these ideas to several molecules or molecular ions.

2. Symmetry elements and operations

A symmetry operation will transform a molecule

into itself so that the transformed molecule will be indistinguishable from the original structure. Also, at least one point in the molecule will be left undisturbed by the transformation. Hence the origin of the name molecular point group. Often, two or more atoms are permuted during the course of the molecular transformation. Since atoms of the same type are indistinguishable, the transformed molecule is indistinguishable from the starting molecule. So, a molecular point group consists of all those symmetry operations that leave a point in the

Dry Lab III: Molecular Symmetry

molecule invariant and permutes identical atoms. 1 Symmetry operations come in several flavours: inversion, reflections, rotations, and improper rotations, and of course no operation at all. The last operation is called the identity operation and is present in all molecules. It is normally denoted by the symbol E. For each symmetry operation there corresponds a symmetry element. More than one operation may correspond to the same symmetry element A rotation operation takes place about a rotation axis. A rotation takes place through an angle of 2 π /n. (By convention, a rotation by a positive angle is considered to be counterclockwise, a rotation through a negative angle would then be clockwise.) Such a rotation is said to be an n-fold rotation. The rotation is about some axis in the molecule called an n-fold rotation axis. If a molecule has more than one rotation axis, the one with the highest value of n is called the principal axis of rotation. 2 The n- fold rotation operation is denoted by C n (plain text) and the axis of rotation is identified by the symbol C n (italics). For example, the water molecule has one principle axis of rotation, a 2- fold axis, C 2 , through the O atom and bisecting the HOH angle. This a rotation by 180 ° , transforming the molecule into itself. In

contrast, the BrF 5 molecule has a 4-fold axis, C 4 , of rotation containing the axial BrF bond. Notice that a 4-fold axis always contains a 2-fold axis. For example, the square planar structure XeF 4 has a C 4 axis through the Xe atom and orthogonal to the plane of the molecule. Carrying out two consecutive 4-fold rotations,

i.e. C 4

conducting a C 2 rotation about the same axis. Therefore, the C 2 axis is coincident with the C 4 axis. In H 2 O, the C 2 axis is the principal axis of rotation. In XeF 4 , the C 4 axis is the principal axis of rotation. For a diatomic molecule, a rotation by any arbitrary angle can be performed about the internuclear axis. Such an axis is

called a C × axis and is the principal axis of rotation.

2

= C 4 C 4 , about a C 4 axis is equivalent to

1 Note that not all identical atoms need be permuted amongst each other. We shall see an

example of this later.
2

The principal axis of rotation need not be unique.

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A reflection takes place in a plane of

symmetry, sometimes called a mirror plane. The reflection operation is denoted by σ (plain) and the mirror plane are both denoted by σ (italics). Normally, reflection planes contain rotation axes or are orthogonal to an axis of rotation. If a

plane is orthogonal to a principal axis of rotation

it is designated by the symbol σ h . If a plane

contains a principal axis of rotation it is usually denoted by σ v . If the plane bisects the angle between two C 2 axes it is called a σ d and such a plane is called a dihedral plane of symmetry. 3 Often, other criteria are needed to distinguish between σ v planes and σ d planes. Water has two reflection planes, both of them σ v planes. In XeF 4 , the reflection plane orthogonal to the C 4 axis (the principal axis) is a σ h plane. An inversion operation, I (sometimes written as i) , through the centre of inversion (I or i) takes the point (x,y,z) in the molecule and transforms it to (-x,-y,-z). The chemical environment at the points (x,y,z) and (x,-y,-z) are identical. Water does not possess an inversion centre whereas XeF 4 does. An n-fold improper rotation, S n , about an n- fold improper rotation axis (same symbol) is composed of two successive transformations:

The first component is an n-fold rotation about S n followed by the second component, a reflection in a plane orthogonal to the S n axis. Note that the n-fold rotation need not correspond to an actual n-fold rotation axis in the molecule. Similarly, the reflection plane orthogonal to the S n axis need not be an actual reflection plane. The water molecule does not possess an improper axis of rotation. A CH 4 molecule has three S 4 axes but no C 4 axis.

3. Symmetry Groups

We use the phrases symmetry groups and molecular point groups synonymously.

A mathematical group, G = {G, }, consists

of a set of elements 4 G = {E, A,B,C,D,

a binary relation, called group multiplication or

}

and

3 Frequently, the σ h plane is called a horizontal plane and the σ v plane is referred to as a vertical reflection plane. There is some danger in doing this since not all σ h planes need be “horizontal” and not all σ v planes need be “vertical.” 4 Do not confuse symmetry elements discussed in section 2 with group elements. The set of symmetry elements do not form a group, only the symmetry operations form a group. The term element used in this definition is standard usage in set theory.

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group product or simply multiplication or

product, denoted by ‘ ’, which satisfies the following properties:

(a) The product of any two elements A and B in

the group is another element in the group, i.e., we write A B G.

(b) If A, B, C are any three elements in the

group then (A B) C = A (B C). Therefore, group multiplication is associative, and frequently, we omit the brackets.

(c) There is a unique element E in G such that

E A=A E=A, for every element A in G. The

element E is called the identity element.

(d) For every element A in G, there is a unique

element X in G, such that X A = A X = E. The element X is referred to as the inverse of A and is denoted A -1 . The identity is its own inverse. The number of elements in a group is called the order of the group. Frequently, it is denoted by the symbol h. Frequently, when no confusion can arise the symbol ‘ ’ for the product is omitted. Also, when there can be no confusion, we will use the symbol G for the group rather than G . If we think of the group elements as symmetry operations of a molecule and if by A B we mean “first we perform the symmetry operation B on the molecule followed by symmetry operation A.” The net result of such consecutive action on a molecule is another symmetry operation. Take dichloromethane as our example. The molecular structure and Cartesian axis system are shown below.

z

x

H H
A
B
y
C
Cl A

Cl B

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Think of the Cartesian axes as being centred at the C atom with the z-axis bisecting the HCH and the ClCCl angles. The x-axis lies in the HCH plane, while the y-axis is in the ClCCl plane. The identity operation, E, leaves the molecule unchanged. The C 2 axis lies along the z-axis. The C 2 operation transforms the dichloromethane molecule as

H
H A
H
H
A
C 2
C
C
l
Cl B
Cl
B Cl
A

A

Carrying out two consecutive C 2 operations is equivalent to the identity transformation. There are two reflection planes in the molecule; both contain the rotation axes. One plane is the plane of the page; containing the ClCCl plane. We denote this plane by σ (yz). The second plane is perpendicular to the plane of the page; denote it by σ (xz). The action of σ (yz) is to give the arrangement of atoms shown below, where the two hydrogen atoms have been interchanged, while the two chlorine atoms and carbon are

H A H
H
H
A
σ (yz)
C
C
Cl
A Cl
Cl
Cl
B
unchanged. The σ (xz) permutes the chlorine
atoms but leaves carbon and the two hydrogen
atoms fixed. This is represented in the
following diagram
H
H
H
H
A
B
σ(xz)
C
C
l
Cl
Cl Cl
A
B
A

Applying the plane σ (yz) twice, i.e., ( σ (yz)) 2 = σ (yz) σ (yz) = E, we get the identity. This means that σ (yz) is its own inverse. Similarly, we find

that ( σ (xz)) 2 = σ (xz) σ (xz) = E, and σ(xz) is its own inverse. Now, if we carry out a σ(xz) reflection first and follow it by a σ (yz) reflection, we get

H

A

H

H

H A

l

B
σ(yz) σ(xz)
C
C

A

Cl

B

Cl

Cl

Comparing this diagram to that of a C 2 rotation

we see that the result is identical. Therefore, we say that

(1)

You can show that performing the reflections in reverse order yields the same result. Note that the symmetry elements remain fixed and are not transformed to new positions when the atoms in the molecule are moved to new positions. What about carrying out a C 2 rotation followed by the

σ(yz)σ(xz) = C 2

reflection σ(yz)? Performing these symmetry

operations yields

H
H
H
H A
B
σ(yz)C 2
C
C
Cl
A Cl
Cl Cl
B
A
which is equivalent to a σ (xz) operation. Show
that carrying out these operations in reverse order
affords the same result. Next, we compute the
product σ(xz)C 2 :
H
A H
H
H B
B
A
σ(xz)C 2
C
C
Cl
Cl
Cl
A Cl
A
B
B

and this is identical with a σ (yz) operation. Again check that the reverse sequence of operations yields the same result. Using the definition of the group and the products of symmetry operations that we have just uncovered, we can construct a group multiplication table:

 C 2v E C 2 σ(xz) σ(yz) EEC 2 σ(xz) σ(yz) C 2 C 2 E σ(yz) σ(xz) σ(xz) σ(xz) σ(yz) E C 2 σ(yz) σ(yz) σ(xz) C 2 E

This table contains all the information about the group and its structure. The name of this molecular point group is C 2v . There are some observations to make about this table. (1) Notice the inner four-by-four box. In each row and each column, each operation appears once and only once. In other words, each row

and each column is a permutation of the others. This is a feature possessed by all group multiplication tables. (2) We can identify smaller groups within the larger one. For example, {E,C 2 } is a group.

A There are two others; what are they? These smaller groups are called subgroups of C 2v .

Dry Lab III: Molecular Symmetry

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(3) In this particular table, we observe that the group product is commutative. This is not necessarily true for other groups.

In the ammonia molecule,
N
H
H

B

the nitrogen atom is the fixed point. The molecule has a C 3 axis of rotation. Note that the both the C 3 and C 3 2 operations occur about the same C 3 axis. There are three reflection planes, each plane containing an NH bond and bisecting the opposing HNH angle. Denote each plane by the number on the hydrogen atom it contains; thus σ 1 is the plane containing H A 1 . This reflection interchanges atoms H B and H C , leaving H A fixed

1

A

H

N

H

3

H C

2

B

σ 1
N
1 H
H
A 2
H
C

3

B

Note that the numbers remain fixed to their original positions. The symmetry elements must not shift with the atoms when they are transformed to new positions. In the previous example, we used labels for the reflection planes that were expressed in terms of the fixed axes external to the molecule. In this example, it is not obvious how to do that. So keep in mind here that the numbers stay fixed and the letters move. You will want to use the double labels whenever it is inconvenient to label axes with references outside the molecule. It is irrelevant whether the numbers stay fixed and the letters move or vice versa. Just be consistent within a given application. Since

σ

each reflection is its own inverse. Since

C 3 3 = C 3 2 C 3 = C 3 C 3 2 = E,

C 3 2 is the inverse of a C 3 rotation (or C 3 is the inverse of C 3 2 ). Recall that a C 3 rotation is a 120 ° rotation in an counterclockwise direction about the rotation axis, while C 3 2 is a 240 ° counterclockwise rotation. Also, we can interpret a C 3 2 rotation as a -120 ° rotation (clockwise). Given these definitions and considerations, here is the complete group multiplication table

1 2 = σ 2 2 = σ 3 2 = E,

 C 3v E C 3 C 3 2 σ 1 σ 2 σ 3 EEC 3 C 3 2 σ 1 σ 2 σ 3 C 3 C 3 C 3 2 E σ 3 σ 1 σ 2 C 3 2 C 3 2 E C 3 σ 2 σ 3 σ 1 σ 1 σ 1 σ 2 σ 3 E C 3 C 3 2 σ 2 σ 2 σ 3 σ 1 C 3 2 E C 3 σ 3 σ 3 σ 1 σ 2 C 3 C 3 2 E

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Exercise 1: Prove the table for C 3v using NH 3 as the sample molecule. (If you use another molecule, the table will basically be the same except some rows and columns may be interchanged.) You will not have to prove all the products. Use the fact that each row

(column) is a permutation of another row

(column) and that no element can occur more

than once in a row or column to assist you. Observe that the group is not commutative.

Exercise 2: The point group of the BrF 5 molecule is C 4v . There are eight symmetry operations in the group. What are they? Construct the group multiplication table. You may use the textbook to assist you.

It is not necessary to derive a group multiplication table each time you want to find

the point group of a molecule or molecular ion.

It is sufficient to determine the presence of only

a particular subset of symmetry elements. Once

you have discovered the molecular point group, the character table for the point group will give you the remaining group operations.

In Atkins, Chapter 15, page 432, follow the Example 15.1 and refer to flow chart in Figure 15.14. As another example, consider ammonia. Is the molecule linear? The answer is no. It has only one axis of rotation, a C 3 axis, which is the principal axis of rotation. Are there C 2 axes orthogonal to the principal axis? The answer is no. Is there a reflection plane orthogonal to the principal axis? Again, the answer is no. Are there three σ v planes containing the C 3 axis and the answer is yes. Therefore, NH 3 must have C 3v symmetry.

Dry Lab III: Molecular Symmetry

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Exercise 3: Determine the molecular point groups for the following species:

(a)

(c)

(e)

(g)

(i)

(j)

(k) cis-Co(NH 3 ) 4 Cl 2 ,

(m) S 4 N 4 ,

When you examine group character tables, you will notice that some of the elements are grouped together. These tables are given on page 951 in Atkins. For example, in the character table for C 3v , we see that the elements are lumped together as

{E,2C 3 ,3 σ v }. That is because the two operations

C 3 and C 3 2 belong to the same class. Similarly,

the three refections belong to the same class. In

a group G={E,A,B,C,

elements A and C are conjugate to each other if

ABA -1 = C,

for some element A in G. An element and all its conjugates form a class. So, for instance, in C 3v ,

if B = C 3 , we have

EC 3 (E) -1 = EC 3 E = C 3 , since E is its own inverse,

C 3 C 3 (C 3 ) -1 = C 3 C 3 C 3 2 = C 3 ,

every element is conjugate to itself,

(C 3 )C 3 (C 3 2 ) -1 = (C 3 )C 3 C 3 = C 3 , and the remaining three can be read from the group multiplication table:

σ 1 C 3 ( σ 1 )

σ 2 C 3 ( σ 2 ) -1 = σ 2 C 3 σ 2 = σ 3 σ 2 = C 3 2 , σ 3 C 3 ( σ 3 ) -1 = σ 3 C 3 σ 3 = σ 1 σ 3 = C 3 , This means that only C 3 and C 3 2 are conjugate to each other and belong to the same class. For the reflections, we have

E

C

C 3 2 σ 1 (C 3 ) -1 = C 3 2 σ 1 C 3 = σ 3 ,

σ 1 σ 1 ( σ 1 )

σ 2 σ 1 ( σ 2 ) -1

σ 3 σ 1 ( σ 3 ) -1 = σ 3 σ 1 σ 3 = C 3 2 σ 3 = σ 1 .

Therefore, the three reflection operations belong in the same class.

Exercise 4: From the group multiplication table that you have worked out for the C 4v group in Exercise 2, determine all the classes. You may confirm your answers by looking in the group character tables on page 951 in Atkins.

 SO 2 , (b) CO 2 , CH 2 =CH 2 , (d) XeF 4 , XeO 2 F 2 , (f) CF 4 , Ni(CO) 4 , (h) Fe 2 (CO) 9 ,

cis-1,2-dicloroethene,

trans-1,2-dichloroethene,

3+

(l) trans-Co(NH 3 ) 4 Cl 2 (n) [Co(NH) 6 ]

}, we say that two

2

2

-1

= σ 1 C 3 σ 1 = σ 2 σ 1 = C 3 ,

σ 1 (E) -1 = E σ 1 E = σ 1 ,

3 σ 1 (C ) -1 = C 3 σ 1 C 3 2 = σ 2 ,

3

2

-1

= σ 1 σ 1 σ 1 = E σ 1 = σ 1 , =

σ 2 σ 1 σ 2 = C 3 σ 2 = σ 1 ,

4. Physical Implications of Symmetry Symmetry is used in a wide variety of ways in chemistry. In quantum chemistry, symmetry is used to classify molecular orbitals and state wave functions. With this classification, we can

Dry Lab III: Molecular Symmetry

simplify calculations of certain matrix elements or expectation values. Often, it is possible to decide when matrix elements or expectation values are zero just on the basis of symmetry alone. In vibrational spectroscopy, frequently,

the vibrational modes of a molecule are classified according to their behaviour under the symmetry operations of the molecular point group. We shall explore some of these ideas in Dry Lab IV. This week we shall examine the connection between symmetry and molecular polarity and molecular chirality. Polarity: The idea here is very simple. A polar molecule has a permanent electric dipole

moment,

dipole moment has a specific orientation in the

molecule. If a molecule has a rotation axis, then the dipole moment must lie along the rotation axis, since no dipole moment can change under a rotation. If a molecule possesses noncoincidental rotation axes, then it can have

no dipole moment since v

along all such rotation axes. This is physically

impossible. Thus, for such molecules v µ = 0 .

If a molecule has a centre of inversion, then it can have no permanent dipole moment. A dipole moment would change sign under inversion and that is not possible physically.

Another way of looking at this is that the dipole moment would have to be a point, and that is not possible for a vector quantity.

Exercise 5: Which of the following molecules in Exercise 3 would have permanent electric dipole moments: (a), (b), (i), (j), (k), (l), (c), (f)?

Chirality: If a molecule is chiral, it is optically active, i.e., it exists in enantiomeric forms. For a molecule to exhibit chirality it must have no improper axes of rotation. Note that S 2 = i and S 1 = σ , a reflection. So if a molecule possesses reflection planes or an inversion centre, it cannot be chiral.

Exercise 6: Which of the following species is chiral? (a) [Co(en) 3 ] 3+ , (b) cis-[Co(en) 2 Cl 2 ] + , (c) trans-[Co(en) 2 Cl 2 ] +

v

µ , which is a vector quantity. The

µ

would have to lie

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